Treatment for fabrics

ABSTRACT

A water-soluble or water-dispersible material for deposition onto a fabric substrate during a treatment process. The material comprises a β 1-4 -linked polysaccharide structure having at least one substituent benefit agent group and optionally, one or more other substituent groups. The average degree of substitution of all substituent groups is from 0.01 to 1.2, preferably from 0.1 to 1.2, more preferably from 0.4 to 1.2. The polysaccharide structure has one or more regions with at least 3, preferably at least 4 consecutive unsubstituted saccharide rings.

This is a division of Ser. No. 09/409,167, filed on Sep. 30, 1999, nowU.S. Pat. No. 6,248,710.

TECHNICAL FIELD

The present invention relates to a material comprising a benefit agentand a deposition aid for deposition of the benefit agent onto a fabric.It further relates to a method of depositing a benefit agent fromsolution or dispersion, onto a fabric.

BACKGROUND OF THE INVENTION

The deposition of a benefit agent onto a fabric is well known in theart. In laundry applications typical “benefit agents” include fabricsofteners and conditioners, soil release polymers, sunscreens; and thelike. Deposition of a benefit agent is used, for example, in fabrictreatment processes such as fabric softening to impart desirableproperties to the fabric substrate.

Conventionally the deposition of the benefit agent may rely upon theattractive forces between the oppositely charged substrate and thebenefit agent. Typically this requires the addition of benefit agentsduring the rinsing step of a treatment process so as to avoid adverseeffects from other charged chemical species present in the treatmentcompositions. For example, cationic fabric conditioners are incompatiblewith anionic surfactants in laundry washing compositions.

Such adverse charge considerations can place severe limitations upon theinclusion of benefit agents in compositions where an active componentthereof is of an opposite charge to that of the benefit agent. Forexample, cotton is negatively charged and thus requires a positivelycharged benefit agent in order for the benefit agent to be substantiveto the cotton, i.e. to have an affinity for the cotton so as to absorbonto it. Often the substantivity of the benefit agent is reduced and/orthe deposition rate of the material is reduced because of the presenceof incompatible charged species in the compositions.

The deterging nature of laundry wash compositions also places severelimitations upon the inclusion of neutral but hydrophobic or oilybenefit agents which are not effectively deposited in the presence ofsurfactant.

Alternatively, when deposition of a conventional benefit agent iseffected by mechanisms that do not rely upon charge interaction but uponother non-covalent forces, for example soil release polymers, otherproblems may occur, namely where interaction of an anionic surfactantwith the benefit agent can also make the material so negatively chargedand/or soluble as to overcome the other attractive interactions.

Furthermore, there is frequently another complication in achievingoptimum deposition of a benefit agent onto a fabric, in that, the needfor solubility of the benefit agent in the medium used to treat thesubstrate is in principle, incompatible with the requirement for of thebenefit agent to deposit/adsorb onto the substrate.

The present invention is directed towards materials for solving one ormore of the above problems.

WO-A-98/00500 discloses detergent compositions comprising a peptide orprotein deposition aid having a high affinity for fibres or a surface,and a benefit agent attached/adsorbed to the deposition aid. However,the peptide or protein is a relatively expensive material and the needstill exists to find a more cost effective alternative material as avehicle for depositing a benefit agent.

Our unpublished copending European Patent Application No. 98300292.4discloses polysaccharide or oligosaccharide conjugates with an attachedentity (e.g. a protein or an enzyme) having a molecular weight of atleast 5,000. Although the poly/oligosaccharide is capable of binding tocellulose, there is no teaching of the molecular requirements foroptimising the balance between water solubility and fabric affinity.

GB-A-948 678 discloses a process for dyeing and printing textiles usingan aqueous preparation containing organic dyestuff residues linked by acovalent bond to high molecular weight polymers such as celluloseethers, cellulose derivatives, starches, gums and other relatednaturally occurring polymers. Cellulose derivatives with a degree ofsubstitution of 0.1 for carboxymethyl substituents are recitedexplicitly. However, these carboxymethyl groups and the dyestuffresidues are not “benefit agent groups” within the sense intendedherein.

U.S. Pat. No. 4,668,779 discloses a gel in the form of a complex betweena metallic oxide and a semi-synthetic polygalactan. This is describedfor use in microbiological analysis. There is no disclosure of chemicalbonding between a substance and the polysaccharide and certainly nosubstituent group which is in any way a benefit agent group forconferring a benefit to a fabric.

U.S. Pat. No. 5,160,641 and U.S. Pat. No. 5,540,850 disclose celluloseether derivatives for use as anti-redeposition agents in fabric washingcompositions. Substantially all of the saccharide rings are substituted.Furthermore, there is no mention of substituents which are themselves,benefit agent groups.

WO-A-95/30042 discloses a gel composition for use in the manufacture oftreated fabrics. It comprises a cellulose based carrier with a solventand a material for conferring a speciality finish, e.g. waterproofing,softening or anti-static effect. However, the speciality finish agent isnot bonded to the cellulosic gel. Further, there is no disclosure orsuggestion of use during washing, rinsing or drying of fabric by aconsumer.

WO-A-98/29528 discloses cellulose ethers in which some substituents are(poly)alkoxylated, analogues of the latter in which the(poly)alkoxylated groups are terminated with a cationic moiety in theform of a quaternary ammonium group, and cellulose ethers in which somesubstituents are carboxylic acids in the salt form (i.e. the materialsare essentially carboxymethylcellulose variants). As defined by thegeneral formulae in WO-A-98/129528, none of these molecules has regionsof unsubstitution, as required by the present invention.

WO-A-99/14245 discloses laundry detergent compositions containingcellulosic based polymers to provide appearance and integrity benefitsto fabrics. These polymers are cellulosic polymers in which thesaccharide rings have pendant oxygen atoms to which substituents ‘R’ canbe hydrogen, lower alkyl or alkylene linkages terminated by carboxylicacid, ester or amide groups. Optionally, up to five alkyleneoxy groupsmay be interspersed between the groups are the respective oxygen atom.WO-A-99/14295 discloses structures analogous to those described inWO-A-99/14245 but in one alternative, the substituents ‘R’ together withthe oxygen on the saccharide ring, constitute pendant half-esters ofcertain dicarboxylic acids. As described in both of these documents,none of the pendant groups is a benefit agent group.

The present invention relates to materials for achieving initialsolubility or dispersibility in the medium used to treat the fabric andeffective deposition of one or more benefit-endowing groups thereon.

DEFINITION OF THE INVENTION

Accordingly, a first aspect of the present invention provides awater-soluble or water-dispersible material for deposition onto a fabricsubstrate during a wash and/or rinse and/or drying process, wherein thematerial comprises a β₁₋₄-linked polysaccharide structure having atleast one substituent benefit agent group and optionally, one or moreother substituent groups, wherein the average degree of substitution ofall substituent groups is from 0.01 to 1.2, preferably from 0.1 to 1.2,more preferably from 0.4 to 1.2, the polysaccharide structure having oneor more regions with at least 3, preferably at least 4 consecutiveunsubstituted saccharide rings.

A second aspect of the present invention also provides a method ofdepositing a benefit agent onto a fabric by its incorporation in amaterial according to the first aspect of the invention and applyingsaid material to the fabric.

A third aspect of the present invention also provides compositionscomprising a material according to the first aspect of the presentinvention. In particular, such compositions preferably comprise one ormore surfactants.

DETAILED DESCRIPTION OF THE INVENTION

The Material

The material of the present invention is water-soluble orwater-dispersible in nature and comprises a β₁₋₄-linked polysaccharidestructure and at least one substituent benefit agent for deposition ontoa fabric during a treatment process.

A polysaccharide comprises a plurality of saccharide rings which havependant hydroxyl groups The benefit agent group(s) and optionally, anyother substituent(s) can be bonded chemically to these hydroxyl groupsby any means described hereinbelow. The “degree of substitution” meansthe average number of substituents per saccharide ring for the totalityof polysaccharide molecules in the sample and is determined for allsaccharide rings whether they form part of a linear backbone or arethemselves pendant side groups in the polysaccharide.

Preferably, the substituent benefit agent group(s) is/are attached tothe polysaccharide by a hydrolytically stable bond. That means that thebonding of the substituted benefit agent(s) should be sufficientlystable so as not to undergo substantial hydrolysis in the environment ofthe treatment process for the duration of that process. For example, inlaundry cleaning applications, the material should be sufficientlystable so that the bond between the benefit and deposition enhancingpart does not undergo hydrolysis in the wash liquor, at the washtemperature, before the benefit agent has been deposited onto thefabric.

Preferably, the bond between the substituent benefit agent(s) and thepolysaccharide is such that the decay rate constant (k_(d)) of thematerial in an aqueous solution at 0.01 wt % of the material togetherwith 0.1 wt % of anionic surfactant at a temperature of 40° C. at a pHof 10.5 is such that k_(d)<10⁻³s⁻¹.

By water-soluble, as used herein, what is meant is that the materialforms an isotropic solution on addition to water or another aqueoussolution.

By water-dispersible, as used herein, what is meant is that the materialforms a finely divided suspension on addition to water or anotheraqueous solution.

Deposition onto a substrate includes deposition by adsorption,co-crystallisation, entrapment and/or adhesion.

Polysaccharide

The β-1,4-linked polysaccharide structure is chosen for having anaffinity for cellulose, viscose and similar fibres. Suitable suchpolysaccharides include cellulose, mannan and glucomannan. It may bestraight or branched. Many naturally occurring polysaccharides have atleast some degree of branching, or at any rate, at least some sacchariderings are in the form of pendant side groups on a main polysaccharidebackbone. The polysaccharide may be charged or uncharged, althoughuncharged types are generally preferred.

The polysaccharide may be a synthetic polysaccharide, a naturallyoccurring polysaccharide or a modified naturally occurringpolysaccharide. Preferably, it has a weight average molecular weight(M_(w)), as determined by GPC, of at least 1,000. In the case ofnaturally occurring polysaccharides, the M_(w) range will be typicallyfrom 100,000 to 2,000,000. For synthetic or modified naturally occurringmaterials, the M_(w) will typically be from 10,000 to 50,000.

Preferably, at least 5% of the saccharide rings are in the consecutiveunsubstituted region(s). Most preferably, at least 80% of theunsubstituted region(s) contain no more than 100, especially no morethan 50 consecutive unsubstituted saccharide rings. For example, no morethan 50% of the saccharide rings are in such regions. Also, for example,no region may have more than 100 (more preferably more than 50)consecutive unsubstituted saccharide rings.

Benefit Agent Group

The benefit agent group may be any group which is used to impartdesirable properties to the fabric upon which the material of thepresent invention is to be deposited. In practice, a material accordingto the present invention may comprise two or more benefit agent groupson the same molecule, either of the same kind or of different kinds.

Preferably, the benefit agent group(s) is/are selected from any of thefollowing:-

(a) fabric softening and/or conditioning agents;

(b) lubricants for inhibition of fibre damage and/or for colour careand/or for crease reduction and/or for ease of ironing;

(c) UV absorbers such as fluorescers and photofading inhibitors, forexample sunscreens/UV inhibitors and/or anti-oxidants;

(d) fungicides and/or insect repellents; and

(e) perfumes.

Suitable fabric softening and/or conditioning agent groups arepreferably chosen from those of the cationic detergent active type, andsilicones. Those of the cationic detergent active type are preferablyselected from quaternary ammonium cationic molecules, for example thosehaving a solubility in water at pH 2.5 and 20° C. of less than 10 g/l.

It is preferred for the ester-linked quaternary ammonium compounds tocontain two or more ester groups. In both monoester and the diesterquaternary ammonium compounds it is preferred if the ester group(s) is alinking group between the nitrogen atom and an alkyl group. The estergroups(s) are preferably attached to the nitrogen atom via anotherhydrocarbyl group.

As used herein the term ‘ester group’, when used in the context of agroup in the quaternary ammonium material, includes an ester group whichis a linking group in the molecule.

Typical are quaternary ammonium compounds containing at least one estergroup, preferably two, wherein at least one higher molecular weightgroup containing at least one ester group and two or three lowermolecular weight groups are linked to a common nitrogen atom to producea cation and wherein the electrically balancing anion is a halide,acetate or lower alkosulphate ion, such as chloride or methosulphate.The higher molecular weight substituent on the nitrogen is preferably ahigher alkyl group, containing 12 to 28, preferably 12 to 22, e.g. 12 to20 carbon atoms, such as coco-alkyl, tallowalkyl, hydrogenatedtallowalkyl or substituted higher alkyl, and the lower molecular weightsubstituents are preferably lower alkyl of 1 to 4 carbon atoms, such asmethyl or ethyl, or substituted lower alkyl. One or more of the saidlower molecular weight substituents may include an aryl moiety or may bereplaced by an aryl, such as benzyl, phenyl or other suitablesubstituents.

More preferably, the quaternary ammonium material comprises a compoundhaving two long chain alkyl or alkenyl chains with an average chainlength equal to or greater than C₁₄. Even more preferably each chain hasan average chain length equal to or greater than C₁₆. Most preferably atleast 50% of each long chain alkyl or alkenyl group has a chain lengthof C₁₈. It is preferred if the long chain alkyl or alkenyl groups arepredominantly linear.

It is particularly advantageous if the cationic softening compound is aquaternary ammonium compound with two C₁₂-C₂₂ alkyl or alkenyl groupsconnected to a quaternary ammonium group via at least one ester link,preferably two ester links, or else a compound with a single long chainwith an average chain length greater than or equal to C₂₀. Examples ofcationic softeners are described in U.S. Pat. No. 4,137,180 andWO-A-93/23510.

The most preferred type of ester-linked quaternary ammonium materialthat can be used as benefit agent group(s) is represented by the formula(A):

wherein R¹, n, R² and X⁻ are as defined above.

It is advantageous for environmental reasons if the quaternary ammoniummaterial is biologically degradable.

Preferred materials of this class such as 1,2 bis[hardenedtallowoyloxy]-3-trimethylammonium propane chloride and their method ofpreparation are, for example, described in U.S. Pat. No. 4,137,180.Preferably these materials comprise small amounts of the correspondingmonoester as described in U.S. Pat. No. 4,137,180 for example 1-hardenedtallow-oyloxy-2-hydroxy-3-trimethylammonium propane chloride.

Another class of preferred ester-linked quaternary ammonium materialsfor use as benefit agent group(s) can be represented by the formula:

wherein each R¹ group is independently selected from C₁₋₄alkyl,hydroxyalkyl or C₂₋₄ alkenyl groups; and wherein each R² group isindependently selected from C₈₋₂₈ alkyl or alkenyl groups; X⁻ is anysuitable counter-ion, i.e. a halide, acetate or lower alkosulphate ion,such as chloride or methosulphate.

n is an integer from 1-5 or is 0

It is especially preferred that each R¹ group is methyl and each n is 2.

Of the compounds of formula (B), Di-(tallowyloxyethyl)-dimethyl ammoniumchloride, available from Hoechst, is the most preferred. Di-(hardenedtallowyloxyethyl)dimethyl ammonium chloride, ex Hoechst anddi-(tallowyloxyethyl)-methyl hydroxyethyl methosulphate are alsopreferred.

Another preferred class of quaternary ammonium cationic fabric softeningagent for use as the benefit agent group(s)is defined by formula (C):-

where R¹, R² and X are as hereinbefore defined.

A preferred material of formula (C) is di-hardened tallow-diethylammonium chloride, sold under the Trademark Arquad 2HT.

It is also possible to use certain mono-alkyl cationic surfactants whichon their own can be used in main-wash compositions for fabrics. Cationicsurfactants that may be used include quatenary ammonium salts of thegeneral formula R₁R₂R₃R₄N⁺X⁻) wherein the R groups are long or shorthydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkylgroups, and X is a counter-ion (for example, compounds in which R₁ is aC₈-C₂₂ alkyl group, preferably a C₈-C₁₀ or C₁₂-C₁₄ alkyl group, R₂ is amethyl group, and R₃ and R₄, which may be the same or different, aremethyl or hydroxyethyl groups); and cationic esters (for example,choline esters).

If the fabric softening and/or conditioning group(s) is/are silicones,these may for example be selected from those disclosed in GB-A-1 549180, EP-A459 821 and EP-A459 822.However, these silicones if used forother benefits listed under the class (b) above, can be regarded as“lubricants”. Other suitable lubricants include any of those known foruse as dye bath lubricants in the textile industry.

Suitable photofading inhibitors of the sunscreen/UV inhibitor type arepreferably molecules with an extinction co-efficient greater than 2000 lmol⁻¹ cm⁻¹ at a wavelength of maximal absorption. Typically for asunscreen maximal absorption occurs at wavelengths of 290-370 nm, moreusually 310-350 nm, especially 330-350 nm.

Examples of suitable sunscreens are given in Cosmetic Science andTechnology Series, Vol. 15; Sunscreens; 2nd edition; edited by Lowe,Shoath and Pathak; Cosmetics and Toiletries; Vol. 102; March 1987; pages21-39; and Evolution of Modern Sunscreen Chemicals; pages 3-35 both byN. A. Saarth.

In particular, suitable sunscreens include carboxylic acids orcarboxylic acid derivatives, for example acrylates, cinnamates andbenzoates or derivatives thereof, such as 4-methoxy cinnamatesalicylates, PABA, 4-acetoxy benzoate dibenzoylmethanes, phenylbenzoimidazoles, aminobenzoates, benzotriazoles and benzophenones.

Suitable photofading inhibitors of the anti-oxidant type includebenzofurans, coumeric acids or derivatives thereof, for example2-carboxy benzofuran and bis(p-amine sulphonates) triazine, DABCOderivatives, tocopherol derivatives, tertiary amines and aromaticsubstituted alcohols eg butylated hydroxytoluene (BHT), Vitamin C(ascorbic acid) and vitamin E.

Suitable fungicides include 6-acetoxy-2,4-dimethyl-m-dioxane,diiodomethyl-p-tolysulphone, 4,4-dimethyloxaolidine,hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, sodiumdimethyldithiocarbamate, sodium 2-mercaptobenzothioazole, zincdimethyldithiocarbamate, zinc 2-mercaptobenzothiazole, sodium2-pyridinethiol-1-oxide, sodium 2-pyridinethiol-1-oxide andN-trichloromethylthio-4-cyclohexene-1,2-dicarboximide.

Suitable insect repellents include N-alkyl neoalkanamides wherein thealkyl is of 1 to 4 carbon atoms and the neoalkanoyl moiety is of 7 to 14carbon atoms preferably N-methyl neodecanamide; N,N-diethyl metatoluamide (DEET), 2-Hydroxyethyl-n-octyl sulphide (MGK 874); N-Octylbicycloheptene dicarboximide (MGK 264); hexahydrodibenzofuran (MGK 11),Di-n-propyl isocinchomerate (MGK 326); 2-Ethyl-1,3-hexanediol,2-(n-butyl)-2-ethyl-1,3-propanediol, dimethyl phthalate, dibutylsuccinate, piperonyl butoxide, pyrethrum, Cornmint, Peppermint, Americanspearmint, Scotch spearmint, Lemon oil, Citronella, cedarwood oil, pineoil, Limonene, carvone, Eucalyptol, Linalool, Gum Camphor, terpineol andfencholic acid.

Suitable perfumes are commercially available and have an undisclosedmolecular structure.

Other Substituents

In addition to the benefit agent group(s), the materials according tothe present invention optionally may also have one or more other pendantgroups. Those are also taken into account when determining the degree ofsubstitution. These may be the same or different and may for example benon-functional groups which are present as artefacts in the naturallyoccurring material or from the process used to obtain a synthetic ormodified naturally occurring material. However, it is possible for oneor more of the non-benefit agent pendant groups to be provided for otherpurposes, e.g. for enhancing the solubility of the molecule. Examples ofsolubility enhancing substituents include carboxyl, sulphonyl, hydroxyl,(poly)ethyleneoxy- and/or (poly)propyleneoxy-containing groups, as wellas amine groups.

The other pendant groups preferably constitute from 0% to 65%, morepreferably from 0% to 10% (e.g. from 0% to 5%) of the total number ofpendant groups. The minimum number of the other pendant groups may, forexample, be 0.1% or 1% of the total. The water-solubilising groups couldcomprise from 0% to 100% of those other groups but preferably from 0% to20%, more preferably from 0% to 10%, still more preferably from 0% to 5%of the total number of other pendant groups.

Synthetic Routes

If the benefit is attached to the deposition polysaccharide this may bechemically bonded via a linking agent. However, direct chemical bondingmay also be used, as described in more detail hereinbelow.

Suitable linking agents are molecules which show a high affinity for thebenefit agent group. It is preferred if the linking agent is covalentlyattached to the backbone of the deposition enhancing part. It is alsoadvantageous if the linking agent is covalently bound to the benefitagent group.

There are basically two general methods for preparing a water-soluble orwater dispersable material comprising a β₁₋₄-linked polysaccharide and asubstituent benefit agent.

According to one such method, the benefit agent(s) is/are grafted ontothe polysaccharide.

In a second alternative method, the benefit agent is grafted onto aprecursor of the β₁₋₄-linked polysaccharide; and then the precursor isconverted into the desired (modified) polysaccharide.

For both methods, the general method for preparing the polysaccharidemay be achieved by a number of different synthetic routes, for example:-

(a) polymerisation of suitable monomers, for example, enzymaticpolymerisation of saccharides, e.g. per S. Shoda, & S. Kobayashi,Makromol. Symp. 1995, 99, 179-184 or oligosaccharide synthesis byorthogonal glycosylation e.g. per H. Paulsen, Angew. Chem. Int. Ed.Engl. 1995, 34 1432-1434.;

(b) derivatisation of a polysaccharide chain (either naturallyoccurring, especially polysaccharides, especially beta-1,4-linkedpolysaccharides, especially cellulose, mannan, glucomannan,galactomannan, xyloglucan; or synthetic polymers) up to the requireddegree of substitution with functional groups, using a reagent(especially acid halides, especially carboxylic acid halides,anhydrides, carboxylic acid anhydrides, carboxylic acids, carbonates) ina solvent which either dissolves the backbone, swells the backbone, ordoes not swell the backbone but dissolves or swells the product).

(c) hydrolysis of polymer derivatives (especially esters) down to therequired degree of substitution; or

(d) a combination of any two or more of routes (a)-(c).

Many suitable β₁₋₄-linked polysaccharides are commercially available.

The degree and pattern of substitution from routes (a) or (c) may besubsequently altered by partial removal of functional groups byhydrolysis or solvolysis or other cleavage. In addition, oralternatively, the degree of polymerisation of the polysaccharide may bereduced before, during, or after the derivatisation with functionalgroups. For example, the relative proportions of reactants and/or thereaction time can be used to control the degree of substitution. Thenumber of unsubstituted regions may be controlled by choice of thesolvent in which the reaction(s) is/are performed, for exampleexploiting the polarity of the solvent and/or the degree to whichreactant are soluble or misable in it (i.e. the degree to which thereaction mixture is homogenous or heterogenous). These techniques andhow to apply then will be readily apparent to those skilled in the artof polymer chemistry. The degree of polymerisation of the polysaccharidemay be increased by further polymerisation or by cross linking agentsbefore, during, or after the derivatisation step.

For both of the aforementioned methods, grafting the benefit agent ontothe polysaccharide can be effected either:-

(a) by physical attraction between the benefit agent and thepolysaccharide, especially the use of a block copolymer where one blockhas a physical affinity for the benefit agent and the other block canundergo a chemical change during treatment which increases its affinityfor the fabric; or

(b) by grafting the benefit agent onto the polysaccharide using a bondwhich is relatively hydrolytically stable. For example, an ester bondcan be used which is more stable than the one intended to undergo thechemical change but which is not be completely stable. For example aconjugated or aromatic ester. Such grafting can be accomplished byreacting the polysaccharide or already-pre-modified polymeric backbone(especially cellulose esters, especially cellulose acetates) with abenefit-agent reagent (especially acid halides, especially carboxylicacid halides, anhydrides, carboxylic acid anhydrides, carboxylic acids,isocyanates, triazine derivatives, amines, hydrazines) in a solventwhich dissolves the polysaccharide, swells the polysaccharide, or doesnot swell the polysaccharide (depending on whether grafting the benefitagent first or last) but dissolves or swells the final product.

For the grafting, typically, radiation methods may be used, forexample:-

1. Grafting by Mutual Irradiation (The Direct Radiation Grafting of theBenefit Group onto the Polysaccharide).

The mutual irradiation method is the simplest radiation-chemical methodfor producing graft copolymers. The procedure involves the irradiationof a polymeric substrate in the presence of a benefit group-containingmonomer solution, preferably in the absence of oxygen at around ambienttemperature for a giving time and irradiation dose. It is known thatmost radiation-initiated polymerization proceeds by free radicalmechanisms, and that it is initiated by the free radicals arising fromthe radiolysis of the either polymer or monomer, although the mutualirradiation is the most efficient method of achieve grafting.

2. Grafting on to Radiation—Peroxided Polysaccharide.

In this method, the polymeric samples of polysaccharide are firstirradiated, typically in the presence of air or pure oxygen atmosphereat around ambient temperature in the absence any monomer or solvent toproduce peroxide or hydroperoxides linkages by gamma irradiation.Subsequently, the graft copolymerization is initiated by the freeradicals produced from the thermal decomposition of peroxide orhydroperoxides linkages under heating with a benefit agent monomer inthe appropriate solvent.

Two different situations arise, depending on whether peroxides orhydroperoxides are formed in the irradiated polymer. Either, theperoxidation leads to peroxidized polymer or else it leads tohydroperoxides.

Grafting may also be effected by means of chemical grafting, for exampleusing ceric ions (A. Habeish et al, J. Appl. Polym. Sci. 1971,15, 11-24)or using other conventional radical initiators such as potassiumpersulphate, e.g. per R. K. Samal, et al J. Polym. Mater. 1987, 4(3),165-172.

In one example hereinbelow there is described a method of producingcarboxymethyl cellulose with grafted fluorescer groups. There are anumber of ways one can introduce fluorescent molecules ontocarboxymethylcellulose. Generally most fluorescent molecules contain anamine functionality. A simple method will be the amidation of these twomolecules. If desired a water soluble coupling agent can also beemployed.

Another method will be via a linking group such as cyanuric chloride(2,4,6-trichloro-1,3,5-triazine) as shown below. This can be conductedby reacting SCMC with cyanuric chloride, followed by reaction with thefluorescent molecule. The reaction sequences can also be altered, i.e.reacting the fluorescent molecule with cyanuric chloride first and thenreacting the adduct with SCMC. As fluorescent molecules are sensitive tolight, the reaction is best to be carried out with a blacked outapparatus.

Compositions

The material according to the first aspect of the present invention maybe incorporated into compositions containing only a diluent (which maycomprise solid and/or liquid) and/or also comprising an activeingredient. The compound is typically included in said compositions atlevels of from 0.01% to 25% by weight, preferably from 0.5% to 20%, mostpreferably from 1% to 15%.

The active ingredient in the compositions is preferably a surface activeagent or a fabric conditioning agent. More than one active ingredientmay be included. For some applications a mixture of active ingredientsmay be used.

The compositions of the invention may be in any physical form e.g. asolid such as a powder or granules, a tablet, a solid bar, a paste, gelor liquid, especially, an aqueous based liquid.

The compositions of the present invention are preferably laundrycompositions, especially main wash (fabric washing) compositions orrinse-added softening compositions. The main wash compositions mayinclude a fabric softening agent and rinse-added fabric softeningcompositions may include surface-active compounds, particularlynon-ionic surface-active compounds, if appropriate.

The detergent compositions of the invention may contain a surface-activecompound (surfactant) which may be chosen from soap and non-soapanionic, cationic, non-ionic, amphoteric and zwitterionic surface-activecompounds and mixtures thereof. Many suitable surface-active compoundsare available and are fully described in the literature, for example, in“Surface-Active Agents and Detergents”, Volumes I and II, by Schwartz,Perry and Berch.

The preferred detergent-active compounds that can be used are soaps andsynthetic non-soap anionic and non-ionic compounds.

The compositions of the invention may contain linear alkylbenzenesulphonate, particularly linear alkylbenzene sulphonates having an alkylchain length of C₈-C₁₅. It is preferred if the level of linearalkylbenzene sulphonate is from 0 wt % to 30 Wt %, more preferably 1 wt% to 25 wt %, most preferably from 2 wt % to 15 wt %.

The compositions of the invention may contain other anionic surfactantsin amounts additional to the percentages quoted above. Suitable anionicsurfactants are well-known to those skilled in the art. Examples includeprimary and secondary alkyl sulphates, particularly C₈-C₁₅ primary alkylsulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylenesulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.Sodium salts are generally preferred.

The compositions of the invention may also contain non-ionic surfactant.Nonionic surfactants that may be used include the primary and secondaryalcohol ethoxylates, especially the C₈-C₂₀ aliphatic alcoholsethoxylated with an average of from 1 to 20 moles of ethylene oxide permole of alcohol, and more especially the C₁₀-C₁₅ primary and secondaryaliphatic alcohols ethoxylated with an average of from 1 to 10 moles ofethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactantsinclude alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

It is preferred if the level of non-ionic surfactant is from 0 wt % to30 wt %, preferably from 1 wt % to 25 wt %, most preferably from 2 wt %to 15 wt %.

Cationic surfactants can also be used for fabric softening and/or rinseconditioning. These may for example be of the type mentionedhereinbefore for use as benefit agent groups.

The choice of surface-active compound (surfactant), and the amountpresent, will depend on the intended use of the detergent composition.In fabric washing compositions, different surfactant systems may bechosen, as is well known to the skilled formulator, for handwashingproducts and for products intended for use in different types of washingmachine.

The total amount of surfactant present will also depend on the intendedend use and may be as high as 60 wt %, for example, in a composition forwashing fabrics by hand. In compositions for machine washing of fabrics,an amount of from 5 to 40 wt % is generally appropriate. Typically thecompositions will comprise at least 2 wt % surfactant e.g. 2-60%,preferably 15-40% most preferably 25-35%.

Detergent compositions suitable for use in most automatic fabric washingmachines generally contain anionic non-soap surfactant, or non-ionicsurfactant, or combinations of the two in any suitable ratio, optionallytogether with soap.

The compositions of the invention, when used as main wash fabric washingcompositions, will generally also contain one or more detergencybuilders. The total amount of detergency builder in the compositionswill typically range from 5 to 80 wt %, preferably from 10 to 60 wt %.

Inorganic builders that may be present include sodium carbonate, ifdesired in combination with a crystallisation seed for calciumcarbonate, as disclosed in GB 1 437 950 (Unilever); crystalline andamorphous aluminosilicates, for example, zeolites as disclosed in GB 1473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473202 (Henkel) and mixed crystalline/amorphous aluminosilicates asdisclosed in GB 1 470 250 (Procter & Gamble); and layered silicates asdisclosed in EP 164 514B (Hoechst). Inorganic phosphate builders, forexample, sodium orthophosphate, pyrophosphate and tripolyphosphate arealso suitable for use with this invention.

The compositions of the invention preferably contain an alkali metal,preferably sodium, aluminosilicate builder. Sodium aluminosilicates maygenerally be incorporated in amounts of from 10 to 70% by weight(anhydrous basis), preferably from 25 to 50 wt %.

The alkali metal aluminosilicate may be either crystalline or amorphousor mixtures thereof, having the general formula:0.8-1.5Na₂O.Al₂O₃.0.8-6SiO₂.

These materials contain some bound water and are required to have acalcium ion exchange capacity of at least 50 mg CaO/g. The preferredsodium aluminosilicates contain 1.5-3.5 SiO₂ units (in the formulaabove). Both the amorphous and the crystalline materials can be preparedreadily by reaction between sodium silicate and sodium aluminate, asamply described in the literature. Suitable crystalline sodiumaluminosilicate ion-exchange detergency builders are described, forexample, in GB 1 429 143 (Procter & Gamble). The preferred sodiumaluminosilicates of this type are the well-known commercially availablezeolites A and X, and mixtures thereof.

The zeolite may be the commercially available zeolite 4A now widely usedin laundry detergent powders. However, according to a preferredembodiment of the invention, the zeolite builder incorporated in thecompositions of the invention is maximum aluminium zeolite P (zeoliteMAP) as described and claimed in EP 384 070A (Unilever). Zeolite MAP isdefined as an alkali metal aluminosilicate of the zeolite P type havinga silicon to aluminium ratio not exceeding 1.33, preferably within therange of from 0.90 to 1.33, and more preferably within the range of from0.90 to 1.20.

Especially preferred is zeolite MAP having a silicon to aluminium rationot exceeding 1.07, more preferably about 1.00. The calcium bindingcapacity of zeolite MAP is generally at least 150 mg CaO per g ofanhydrous material.

Organic builders that may be present include polycarboxylate polymerssuch as polyacrylates, acrylic/maleic copolymers, and acrylicphosphinates; monomeric polycarboxylates such as citrates, gluconates,oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates;and sulphonated fatty acid salts. This list is not intended to beexhaustive.

Especially preferred organic builders are citrates, suitably used inamounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylicpolymers, more especially acrylic/maleic copolymers, suitably used inamounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt %.

Builders, both inorganic and organic, are preferably present in alkalimetal salt, especially sodium salt, form.

Compositions according to the invention may also suitably contain ableach system. Fabric washing compositions may desirably contain peroxybleach compounds, for example, inorganic persalts or organicperoxyacids, capable of yielding hydrogen peroxide in aqueous solution.

Suitable peroxy bleach compounds include organic peroxides such as ureaperoxide, and inorganic persalts such as the alkali metal perborates,percarbonates, perphosphates, persilicates and persulphates. Preferredinorganic persalts are sodium perborate monohydrate and tetrahydrate,and sodium percarbonate.

Especially preferred is sodium percarbonate having a protective coatingagainst destabilisation by moisture. Sodium percarbonate having aprotective coating comprising sodium metaborate and sodium silicate isdisclosed in GB 2 123 044B (Kao).

The peroxy bleach compound is suitably present in an amount of from 0.1to 35 wt %, preferably from 0.5 to 25 wt %. The peroxy bleach compoundmay be used in conjunction with a bleach activator (bleach precursor) toimprove bleaching action at low wash temperatures. The bleach precursoris suitably present in an amount of from 0.1 to 8 wt %, preferably from0.5 to 5 wt %.

Preferred bleach precursors are peroxycarboxylic acid precursors, moreespecially peracetic acid precursors and pernoanoic acid precursors.Especially preferred bleach precursors suitable for use in the presentinvention are N,N,N′,N′,-tetracetyl ethylenediamine (TAED) and sodiumnoanoyloxybenzene sulphonate (SNOBS). The novel quaternary ammonium andphosphonium bleach precursors disclosed in U.S. Pat. No. 4,751,015 andU.S. 4,818,426 (Lever Brothers Company) and EP 402 971A (Unilever), andthe cationic bleach precursors disclosed in EP 284 292A and EP 303 520A(Kao) are also of interest.

The bleach system can be either supplemented with or replaced by aperoxyacid. examples of such peracids can be found in U.S. Pat. No.4,686,063 and U.S. 5,397,501 (Unilever). A preferred example is theimido peroxycarboxylic class of peracids described in EP A 325 288, EP A349 940, DE 382 3172 and EP 325 289. A particularly preferred example isphtalimido peroxy caproic acid (PAP). Such peracids are suitably presentat 0.1-12%, preferably 0.5-10%.

A bleach stabiliser (transition metal sequestrant) may also be present.Suitable bleach stabilisers include ethylenediamine tetra-acetate(EDTA), the polyphosphonates such as Dequest (Trade Mark) andnon-phosphate stabilisers such as EDDS (ethylene diamine di-succinicacid). These bleach stabilisers are also useful for stain removalespecially in products containing low levels of bleaching species or nobleaching species.

An especially preferred bleach system comprises a peroxy bleach compound(preferably sodium percarbonate optionally together with a bleachactivator), and a transition metal bleach catalyst as described andclaimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).

The compositions according to the invention may also contain one or moreenzyme(s). Suitable enzymes include the proteases, amylases, cellulases,oxidases, peroxidases and lipases usable for incorporation in detergentcompositions. Preferred proteolytic enzymes (proteases) are,catalytically active protein materials which degrade or alter proteintypes of stains when present as in fabric stains in a hydrolysisreaction. They may be of any suitable origin, such as vegetable, animal,bacterial or yeast origin.

Proteolytic enzymes or proteases of various qualities and origins andhaving activity in various pH ranges of from 4-12 are available and canbe used in the instant invention.

Examples of suitable proteolytic enzymes are the subtilins which areobtained from particular strains of B. Subtilis B. licheniformis, suchas the commercially available subtilisins Maxatase (Trade Mark), assupplied by Gist Brocades N.V., Delft, Holland, and Alcalase (TradeMark), as supplied by Novo Industri A/S, Copenhagen, Denmark.

Particularly suitable is a protease obtained from a strain of Bacillushaving maximum activity throughout the pH range of 8-12, beingcommercially available, e.g. from Novo Industri A/S under the registeredtrade-names Esperase (Trade Mark) and Savinase (Trade-Mark). Thepreparation of these and analogous enzymes is described in GB 1 243 785.Other commercial proteases are Kazusase (Trade Mark obtainable fromShowa-Denko of Japan), Optimase (Trade Mark from Miles Kali-Chemie,Hannover, West Germany), and Superase (Trade Mark obtainable from Pfizerof U.S.A.).

Detergency enzymes are commonly employed in granular form in amounts offrom about 0.1 to about 3.0 wt %. However, any suitable physical form ofenzyme may be used.

The compositions of the invention may contain alkali metal, preferablysodium carbonate, in order to increase detergency and ease processing.Sodium carbonate may suitably be present in amounts ranging from 1 to 60wt %, preferably from 2 to 40 wt %. However, compositions containinglittle or no sodium carbonate are also within the scope of theinvention.

Powder flow may be improved by the incorporation of a small amount of apowder structurant, for example, a fatty acid (or fatty acid soap), asugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.One preferred powder structurant is fatty acid soap, suitably present inan amount of from 1 to 5 wt %.

Other materials that may be present in detergent compositions of theinvention include sodium silicate; antiredeposition agents such ascellulosic polymers; soil release polymers; inorganic salts such assodium sulphate; lather control agents or lather boosters asappropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles;perfumes; foam controllers; fluorescers and decoupling polymers. Thislist is not intended to be exhaustive. However, many of theseingredients will be better delivered as benefit agent groups inmaterials according to the first aspect of the invention.

The detergent composition when diluted in the wash liquor (during atypical wash cycle) will typically give a pH of the wash liquor from 7to 10.5 for a main wash detergent.

Particulate detergent compositions are suitably prepared by spray-dryinga slurry of compatible heat-insensitive ingredients, and then sprayingon or post-dosing those ingredients unsuitable for processing via theslurry. The skilled detergent formulator will have no difficulty indeciding which ingredients should be included in the slurry and whichshould not.

Particulate detergent compositions of the invention preferably have abulk density of at least 400 g/l, more preferably at least 500 g/l.Especially preferred compositions have bulk densities of at least 650g/liter, more preferably at least 700 g/liter.

Such powders may be prepared either by post-tower densification ofspray-dried powder, or by wholly non-tower methods such as dry mixingand granulation; in both cases a high-speed mixer/granulator mayadvantageously be used. Processes using high-speed mixer/granulators aredisclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP420 317A (Unilever).

Liquid detergent compositions can be prepared by admixing the essentialand optional ingredients thereof in any desired order to providecompositions containing components in the requisite concentrations.Liquid compositions according to the present invention can also be incompact form which means it will contain a lower level of water comparedto a conventional liquid detergent.

Treatment

The treatment of the fabric with the material of the invention can bemade by any suitable method such as washing, soaking or rinsing of thefabric.

Typically the treatment will involve a washing or rinsing method such astreatment in the main wash or rinse cycle of a washing machine andinvolves contacting the fabric with an aqueous medium comprising thematerial of the invention.

The present invention will now be explained in more detail by referenceto the following non-limiting examples:-

EXAMPLE 1 Preparation of Carboxymethyl Cellulose with Pendant FluorescerGroups

Carboxymethylcellulose (medium viscosity) (2 g) was dissolved in water(100 ml) and the pH of the solution was adjusted to 5. Then in a blackedout apparatus, cyanuric chloride (1 g) was added dropwise at 5° C. overa slow stream of nitrogen. The reaction mixture was stirred for one hourat this temperature. It was then allowed to rise to ambient temperatureand then an aqueous suspension of4—4′-bis[4-amino-6-(4-carboxyethylanilino)-s-triazine-2-yl)amino]2,2′-stilbenedisulphonicacid disodium salt (a fluorescent molecule) (0.2 g) was added dropwiseover 5 minutes period. After the addition was complete, the temperaturewas raised to 40° C. and the reaction mixture was stirred overnight atthis temperature. The reaction product was transferred to a blacked outcrystallising dish and freeze dried. This produced a fluorescentfunctionalised SCMC.

This material was found by analysis to have a degree of substitution andregions of consecutive ring unsubstitution within claim 1.

EXAMPLE 2 Preparation of Guar Gum with Pendant UV Absorber Groups

2 g Guar gum was dissolved in 1 liter of rapidly stirred hot distilledwater. The solution was allowed to cool to room temperature. 0.01 gsodium periodate in 50 ml distilled water as added to the guar gumsolution and stirred for 72 hours.

100 ml of the oxidised guar gum solution was acidified to pH 6 and 0.2gram p-nitrophenyl hydrazine (a UV absorber) in 5ml methanol in wasadded. The solution was stirred for 48 hours.

Precipitating the aqueous solution into ethanol purified the polymer.The precipitate was filtered off and re-dissolved in distilled waterwithout drying. This process was repeated three times. The purifiedpolymer was dissolved in distilled water and the solid contentdetermined. The level of p-nitrophenyl hydrazine was determined byUV/vis spectroscopy.

This material was found by analysis to have a degree of substitution andregions of consecutive ring unsubstitution within claim 1.

EXAMPLE 3 Performance Evaluation—Deposition onto White Cotton

A stock solution comprising of 0.05 g surfactant, 0.02 g (1.86% tag) ofthe substituted polymer of Example 1 was made up to 100 ml using 0.01Msodium bicarbonate. Three systems were evaluated, 100% LAS, 75% LAS/25%Synperonic A7 and when no surfactant was used.

Mercerised white cotton (1 gram) was washed in 10ml stock solution at40° C for 30 minutes. After the wash period, excess liquor was removedby spin-drying. The amount of tagged polymer in solution after washingdetermined by UV/vis spectroscopy at 390 nm using the stock solution asreference.

The following Table shows that build up of the polymer milligrams pergram of cotton fabric over a number of wash cycles.

100% 75% LAS/ No Number of LAS 25% A7 surfactant washes mg polymer pergram cotton 0 0 0 0 1 0.016 −0.005 0.485 2 0.13 0.187 0.745 3 0.1620.277 0.855 4 0.23 0.497 1.049 5 0.457 0.722 1.068

The composition examples 4-15, were each prepared in two variants, the“Polymer” being either the product of Example 1 or the product ofExample 2.

EXAMPLE 4 Spray-Dried Powder

Component % w/w Na PAS 11.5 Dobanol 25-7 6.3 Soap 2.0 Zeolite 24.1 SCMC0.6 Na Citrate 10.6 Na Carbonate 23.0 Polymer 4.0 Silicone Oil 0.5Dequest 2066 0.4 Sokalan CP5 0.9 Savinase 16L 0.7 Lipolase 0.1 Perfume0.4 Water/salts to 100

EXAMPLE 5 Detergent Granulate Prepared by Non-Spray Drying Method

The following composition was prepared by the two-stage mechanicalgranulation method described in EP-A-367 339.

Component % w/w Na PAS 13.5 Dobanol 25-7 2.5 STPP 45.3 Na Carbonate 4.0Polymer 3.8 Na Silicate 10.1 Minors 1.5 Water balance

EXAMPLE 6 Isotropic Laundry Liquid

Component % w/w Na-citrate (37.5%) 10.7 Propyleneglycol 7.5 EthyleneGlycol 4.5 Borax 3.0 Savinase 16L 0.3 Lipolase 0.1 Polymer 3.5Monoethanolamine 0.5 Cocofatty acid 1.7 NaOH (50%) 2.2 LAS 10.3 Dobanol25-7 6.3 LES 7.6 Minors 1.3 (adjust pH to 7 with NaOH) Water up to 100

EXAMPLE 7 Structured Laundry Liquid

Component % w/w LAS 16.5 Dobanol 25-7 9 Oleic acid (Priolene 6907) 4.5Zeolite 15 KOH, neutralisation of acids and pH to 8.5 Citric acid 8.2deflocculating polymer 1 Protease 0.38 Lipolase 0.2 Polymer 2.0 Minors0.4 Water to 100%

% w/w Component Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Naalcohol EO sulphate 0.0 0.0 0.0 0.0 0.0 0.0 0.0 13.3 linearalkylbenzenesulfonate, Na salt (LAS) 5.1 5.9 5.8 7.3 8.2 9.9 23.7 7.6sodium stearate 0.0 0.3 0.3 0.3 1.0 1.2 0.0 0.0 fatty acid 1.7 0.3 0.30.4 0.0 0.0 0.0 0.0 alcohol ethoxylate 9EO 0.0 0.0 0.0 0.0 0.0 0.0 0.07.6 alcohol ethoxylate 7EO branched 2.5 3.9 3.9 4.8 4.3 5.2 0.0 0.0alcohol ethoxylate 3EO branched 3.4 2.9 2.9 3.6 2.3 2.8 0.0 0.0 sodiumcitrate 0.0 0.0 0.0 0.0 3.3 7.4 0.0 4.8 propylene glycol 0.0 0.0 0.0 0.00.0 0.0 0.0 6.4 sorbitol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4.3 sodium borate0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.9 sodium silicate 0.4 5.9 5.8 7.3 1.5 0.07.9 0.0 sodium carbonate 17.6 9.0 12.0 12.4 9.2 17.5 17.3 0.0 sodiumbicarbonate 0.0 0.0 0.0 6.1 0.9 3.8 0.0 0.0 sodium sulphate 19.8 16.213.9 16.3 0.0 0.0 26.1 0.0 STPP 0.0 22.1 22.1 27.4 0.0 0.0 14.3 0.0zeolite A24 (anhydrous) 19.8 0.0 0.0 0.0 28.0 33.8 0.0 0.0 sodiumperborate tetrahydrate 11.7 17.9 17.8 0.0 0.0 0.0 0.0 0.0 coatedpercarbonate 13.5 avOx 0.0 0.0 0.0 0.0 18.0 0.0 0.0 0.0 TAED granule(83%) 2.1 2.0 2.0 0.0 5.2 0.0 0.0 0.0 minors 5.9 3.8 3.2 4.2 8.0 8.3 0.81.2 water 0.0 0.0 0.0 0.0 0.0 0.0 0.0 46.9 polymer 10.0 10.0 10.0 10.010.0 10.0 10.0 5.0 TOTAL: 100.0 100.0 100.0 100.0 100.0 100.0 100.0100.0

Raw Material Specification

Component Specification Polymer The material of Example 1 LAS LinearAlkyl Benzene Sulphonic-acid, Marlon AS3, ex Huls Na-LAS LAS-acidneutralised with NaOH Dobanol 25-7 C12-15 ethoxylated alcohol, 7EO, exShell LES Lauryl Ether Sulphate, Dobanol 25-S3, ex Shell ZeoliteWessalith P, ex Degussa STPP Sodium Tri PolyPhosphate, Thermphos NW, exHoechst Dequest 2066 Metal chelating agent, ex Monsanto Silicone oilAntifoam, DB 100, ex Dow Corning Tinopal CBS-X Fluorescer, ex Ciba-GeigyLipolase Type 100L, ex Novo Savinase 16L Protease, ex Novo Sokalan CP5Acrylic/Meleic Builder Polymer ex BASF Deflocculating Polymer PolymerA-l-l disclosed in EP-A- 346 995 SCMC Sodium Carboxymethyl Cellulose

What is claimed is:
 1. A water-soluble or water-dispersible material fordeposition onto a fabric substrate during a wash, rinse, and dryingprocess, wherein the material comprises a β₁₋₄-linked polysaccharidestructure having at least one substitutent benefit agent group, whereinthe average degree of substitution of all substitutent groups is from0.1 to 1.2, the polysaccharide structure having one or more regions withat least 3 consecutive unsubstituted saccharide rings; and wherein thebenefit agent group is selected from: (a) fabric softening andconditioning agents; (b) lubricants; (c) fungicides, insect repellentsand insecticides; and (d) perfumes.
 2. The material of claim 1 whereinthe average degree of substitution for all substituent groups is from0.4 to 1.2.
 3. The material of claim 1 wherein the polysaccharidestructure has one or more regions with at least 4 consecutiveunsubstituted saccaharide rings.
 4. The material of claim 1, wherein atleast 5% of the saccharide rings are in said consecutive unsubstitutedregion(s).
 5. The material of claim 1, wherein no more than 50% of thesaccharide rings are in said consecutive unsubstituted regions.
 6. Thematerial of claim 1, wherein at least 80% of said unsubstituted regionshave no more than 100 consectutive unsubstituted saccharide rings. 7.The material of claim 1, wherein at least 80% if said unsubstitutedregions have no more than 50 consecutive unsubstituted saccharide rings.8. The material of claim 1, wherein from 0% to 65% of the number oftotal pendant groups are other than benefit agent groups.
 9. Thematerial of claim 1, wherein from 0% to 10% of the number of totalpendant groups other than benefit agent groups.
 10. The material ofclaim 9, wherein from 0% to 20% of the other groups are watersolubilizing groups.
 11. The material of claim 9, wherein from 0% to 10%of the other groups are water-solubilizing groups.
 12. The material ofclaim 9, wherein from 0% to 5% of the other groups arewater-solubilizing groups.
 13. A composition comprising the material ofclaim 1 and at least one further component.
 14. The composition of claim13, in which the further component comprises a surfactant.
 15. Thecomposition of claim 13, comprising from 0.01% to 25% by weight of thematerial of claim
 1. 16. The composition of claim 15 comprising from0.5% to 20% by weight of the material of claim
 1. 17. The composition ofclaim 13 comprising from 1% to 15% by weight of the material of claim 1.18. A method of depositing a benefit agent onto a fabric substrate by:(a) preparing a liquor comprising the material of claim 1; and (b)treating the substrate with said liquor.